甘露糖月桂酸酯的酶法合成及其性质研究
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摘要
糖酯是一类用可再生资源合成的非离子型表面活性剂。该类物质具有两亲结构,无毒,可以100%被生物降解,是公认的环保“绿色”产品,在食品、化妆品、医药工业中具有十分广阔的应用前景。本文以甘露糖和月桂酸为原料,在有机相中通过脂肪酶催化合成甘露糖月桂酸酯。
首先对甘露糖酯的分析检测和分离纯化方法进行了研究。确定了甘露糖酯的薄层色谱(TLC)定性分析条件:采用正己烷/乙酸乙酯(1:1, v/v)和甲醇二次展开,可以有效地将单酯、二酯Ⅰ、二酯Ⅱ和二酯Ⅲ分开,它们的Rf分别为0.13、0.26和0.43和0.59。将TLC条件应用到硅胶柱层析,并采用梯度洗脱的方法分离纯化甘露糖酯,洗脱剂依次为:1000 mL乙酸乙酯/正己烷(1:1, v/v),1000 mL乙酸乙酯/正己烷(6:4, v/v),1000 mL乙酸乙酯/正己烷/甲醇(7:2:1, v/v/v),500 mL乙酸乙酯/正己烷/甲醇(4:2:4, v/v/v),500 mL甲醇,并用薄层层析检测产物,再收集。分离纯化的甘露糖酯分别采用HPLC、HPLC-MS和NMR进行定性和定量分析,确定酶法合成产物中有6-O-甘露糖月桂酸酯、1,6-di-O-甘露糖月桂酸酯、4,6-di-O-甘露糖月桂酸酯和3,6-di-O-甘露糖月桂酸酯。
设计了同时反应-萃取体系(SRE)进行二酯的酶法选择性合成。通过单因素实验,确定了有机相脂肪酶催化合成甘露糖月桂酸二酯的最佳工艺条件:以正己烷和乙腈作为合成甘露糖月桂酸酯的反应溶剂,甘露糖的浓度为0.05 mol/L,脂肪酶添加量为15 mg/mL,相比为7.5:7.5(v/v),酸醇摩尔比为4:1,分子筛添加量为60 mg/mL,50℃振荡水浴反应72 h,甘露糖月桂酸二酯的转化率达到51.2%,此时单酯的转化率为25.3%,总酯转化率显著高于丙酮单相体系的总酯转化率。
研究了甘露糖酯作为表面活性剂的一些基本性质如溶解性、HLB值、临界胶束浓度、起泡性和乳化性以及美拉德反应活性。结果显示甘露糖酯是一种表面活性较好的物质,甘露糖二酯HLB值均为8~9左右,可作为润湿剂和铺展剂,单酯的HLB为11.22,可以作为O/W型乳化剂。单酯的起泡能力、乳化能力和乳化稳定性都要好于二酯,而泡沫稳定性弱于二酯,将单酯和二酯进行复配可以提高其乳化性能和起泡性能。研究了甘露糖酯的美拉德反应活性,发现1,6-di-O-甘露糖月桂酸酯由于半缩醛羟基已经被取代,其Maillard反应活性很低,进一步验证了二酯的结构。
Carbohydrate fatty acid esters can be synthesized from renewable sources. The main properties of these compounds are their biodegradability and nontoxicity. They have hydrophilic-lipophilic structure and play an important role in non-ionic surfactants because they are environmental protective. Now they have been widely used in food, pharmaceutical industries and cosmetic. In this paper lauroyl mannose was synthesized by lauric acid and mannose.
The methods of detection and separation were firstly studied. The analysis condition for the TLC was confirmed, n-hexane: ethyl acetate(1:1, v/v)and methanol were used as mobile phase. The monoester, diesterⅠ, diesterⅡand diesterⅢcould be separated effectively. The retention factor(Rf)were 0.13、0.26、0.43and 0.59 respectively.
Then the condition of TLC was applied to silica gel column chromatography for separating and purifying the lauroyl mannose: 1000 mL ethyl acetate/n-hexane(1:1, v/v)、1000 mL ethyl acetate/n-hexane(6:4, v/v)、1000 mL ethyl acetate/n-hexane/methanol(7:2:1, v/v/v)、500 mL ethyl acetate/n-hexane/methanol(4:2:4, v/v/v)and 500 mL methanol were used as mobile phase. The separated products were identified by HPLC, HPLC-MS and NMR. It was certain that the product consisted of 6-O-lauryl mannose mannose, 1,6-di-O-lauryl mannose, 4,6-di-O-lauryl mannose, and 3,6-di-O-lauryl mannose.
In order to synthesize diesters selectively, simultaneous reaction and solvent extraction system(SRE)was designed. The optimal condition for biphasic system was as follows: Diester productivity of 51.2% and monoester productivity of 25.3% were obtained under such conditions as the amount of mannose 0.05 mol/L, lipase 15 mg/mL, the phase ratio n-hexane:acetonitrile 7.5:7.5(v/v), the molar ratio of lauric acid to mannose 4:1, the amount of molecular sieve 60 mg/mL, the temperature 50℃, the shaking speed of the water bath 150 r/min, and the reaction time 72 h. The fractional conversion of lauroyl mannose was much higher than that in acetone system.
The surfactant properties of monoester and diesters were also studied. The solubility, HLB, critical micelle concentration, foaming ability, foam stability, emulsifying ability, emulsion stability and also the Maillard reaction. The result showed that lauroyl mannoses had good surface activity. The HLB of diesters were all about 8~9, which could be used as wetting agent, while the HLB of monoester was 11.22 which could be used as O/W emulsifier. The foaming ability, foam stability, emulsifying ability and emulsion stability of monoester were better than diesters’but not so good in foam stability. The foaming property and emulsifying property became better while mixing diester and monoester together. It showed 1,6-di-O-lauryl mannose retarded Maillard reaction. The structures of diesters were identified further.
首先对甘露糖酯的分析检测和分离纯化方法进行了研究。确定了甘露糖酯的薄层色谱(TLC)定性分析条件:采用正己烷/乙酸乙酯(1:1, v/v)和甲醇二次展开,可以有效地将单酯、二酯Ⅰ、二酯Ⅱ和二酯Ⅲ分开,它们的Rf分别为0.13、0.26和0.43和0.59。将TLC条件应用到硅胶柱层析,并采用梯度洗脱的方法分离纯化甘露糖酯,洗脱剂依次为:1000 mL乙酸乙酯/正己烷(1:1, v/v),1000 mL乙酸乙酯/正己烷(6:4, v/v),1000 mL乙酸乙酯/正己烷/甲醇(7:2:1, v/v/v),500 mL乙酸乙酯/正己烷/甲醇(4:2:4, v/v/v),500 mL甲醇,并用薄层层析检测产物,再收集。分离纯化的甘露糖酯分别采用HPLC、HPLC-MS和NMR进行定性和定量分析,确定酶法合成产物中有6-O-甘露糖月桂酸酯、1,6-di-O-甘露糖月桂酸酯、4,6-di-O-甘露糖月桂酸酯和3,6-di-O-甘露糖月桂酸酯。
设计了同时反应-萃取体系(SRE)进行二酯的酶法选择性合成。通过单因素实验,确定了有机相脂肪酶催化合成甘露糖月桂酸二酯的最佳工艺条件:以正己烷和乙腈作为合成甘露糖月桂酸酯的反应溶剂,甘露糖的浓度为0.05 mol/L,脂肪酶添加量为15 mg/mL,相比为7.5:7.5(v/v),酸醇摩尔比为4:1,分子筛添加量为60 mg/mL,50℃振荡水浴反应72 h,甘露糖月桂酸二酯的转化率达到51.2%,此时单酯的转化率为25.3%,总酯转化率显著高于丙酮单相体系的总酯转化率。
研究了甘露糖酯作为表面活性剂的一些基本性质如溶解性、HLB值、临界胶束浓度、起泡性和乳化性以及美拉德反应活性。结果显示甘露糖酯是一种表面活性较好的物质,甘露糖二酯HLB值均为8~9左右,可作为润湿剂和铺展剂,单酯的HLB为11.22,可以作为O/W型乳化剂。单酯的起泡能力、乳化能力和乳化稳定性都要好于二酯,而泡沫稳定性弱于二酯,将单酯和二酯进行复配可以提高其乳化性能和起泡性能。研究了甘露糖酯的美拉德反应活性,发现1,6-di-O-甘露糖月桂酸酯由于半缩醛羟基已经被取代,其Maillard反应活性很低,进一步验证了二酯的结构。
Carbohydrate fatty acid esters can be synthesized from renewable sources. The main properties of these compounds are their biodegradability and nontoxicity. They have hydrophilic-lipophilic structure and play an important role in non-ionic surfactants because they are environmental protective. Now they have been widely used in food, pharmaceutical industries and cosmetic. In this paper lauroyl mannose was synthesized by lauric acid and mannose.
The methods of detection and separation were firstly studied. The analysis condition for the TLC was confirmed, n-hexane: ethyl acetate(1:1, v/v)and methanol were used as mobile phase. The monoester, diesterⅠ, diesterⅡand diesterⅢcould be separated effectively. The retention factor(Rf)were 0.13、0.26、0.43and 0.59 respectively.
Then the condition of TLC was applied to silica gel column chromatography for separating and purifying the lauroyl mannose: 1000 mL ethyl acetate/n-hexane(1:1, v/v)、1000 mL ethyl acetate/n-hexane(6:4, v/v)、1000 mL ethyl acetate/n-hexane/methanol(7:2:1, v/v/v)、500 mL ethyl acetate/n-hexane/methanol(4:2:4, v/v/v)and 500 mL methanol were used as mobile phase. The separated products were identified by HPLC, HPLC-MS and NMR. It was certain that the product consisted of 6-O-lauryl mannose mannose, 1,6-di-O-lauryl mannose, 4,6-di-O-lauryl mannose, and 3,6-di-O-lauryl mannose.
In order to synthesize diesters selectively, simultaneous reaction and solvent extraction system(SRE)was designed. The optimal condition for biphasic system was as follows: Diester productivity of 51.2% and monoester productivity of 25.3% were obtained under such conditions as the amount of mannose 0.05 mol/L, lipase 15 mg/mL, the phase ratio n-hexane:acetonitrile 7.5:7.5(v/v), the molar ratio of lauric acid to mannose 4:1, the amount of molecular sieve 60 mg/mL, the temperature 50℃, the shaking speed of the water bath 150 r/min, and the reaction time 72 h. The fractional conversion of lauroyl mannose was much higher than that in acetone system.
The surfactant properties of monoester and diesters were also studied. The solubility, HLB, critical micelle concentration, foaming ability, foam stability, emulsifying ability, emulsion stability and also the Maillard reaction. The result showed that lauroyl mannoses had good surface activity. The HLB of diesters were all about 8~9, which could be used as wetting agent, while the HLB of monoester was 11.22 which could be used as O/W emulsifier. The foaming ability, foam stability, emulsifying ability and emulsion stability of monoester were better than diesters’but not so good in foam stability. The foaming property and emulsifying property became better while mixing diester and monoester together. It showed 1,6-di-O-lauryl mannose retarded Maillard reaction. The structures of diesters were identified further.
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